CN102704040A - Preparation method of high strength carbon fibers - Google Patents
Preparation method of high strength carbon fibers Download PDFInfo
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- CN102704040A CN102704040A CN2012101531988A CN201210153198A CN102704040A CN 102704040 A CN102704040 A CN 102704040A CN 2012101531988 A CN2012101531988 A CN 2012101531988A CN 201210153198 A CN201210153198 A CN 201210153198A CN 102704040 A CN102704040 A CN 102704040A
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Abstract
A preparation method of the high strength carbon fibers relates to the technical field of preparation of carbon fibers. The preparation method includes controlling oxygen volume concentration of hot oxygen stabilization atmosphere to be 21.8+-1% to prepare the high strength carbon fibers according to the fact that cyclizing degree of hot oxygen stabilization fibers is 82+-5% and aromatization index is 65+-5%. The tensile strength of the carbon fibers can exceed 3.75GPa.
Description
Technical field
The invention belongs to the preparing technical field of carbon fiber; Relate to a kind of method for preparing high-strength carbon fiber; Especially with the cyclisation degree (η) of thermal oxidation stability chemical fibre dimension be 82 ± 5% and aromatisation index (AI) be 65 ± 5% serve as to regulate and control foundations; The oxysome volume concentrations of control thermal oxidation stability gasification atmosphere is 21.8 ± 1%, obtains the thermal oxidation stability chemical fibre dimension of high-quality, thereby makes the above high-strength carbon fibre of 3.75GPa.
Background technology
The inhomogeneities of fibrous inside radial structure is one of key factor of restriction carbon fiber TENSILE STRENGTH, is embodied in the TENSILE STRENGTH cortex height of carbon fiber and core is low.This kind defective is mainly derived from two stages: the one, and the spinning stage is owing to the different precursor formation skin-core structures that make of fiber freezing rate radially and solvent diffuse speed; The 2nd, in the thermal oxidation stability stage, cause the degree of oxidation of PAN fibrocortex to be significantly higher than core owing to fiber double diffusion speed radially is different.Double diffusion in the thermal oxidation stability process, be meant volatile small molecule that oxygen produces by diffusion of export-oriented fibrous inside and reaction from reaction environment from fibrous inside to external diffusion.Along with reaction is carried out; Thermal oxidation stability chemical fibre dimension skin zone combines probability far above core with oxygen; Cause the top layer of fiber to form compact oxide; Oxygen in the reaction atmosphere enters into fibrous inside and participates in the probability of reaction and greatly reduce, and the fiber radially PAN macromolecular chain extent of reaction is different and further form skin-core structure.Skin-core structure can be delivered to through carbonisation and form the radial structure defective in the carbon fiber, thereby reduces the mechanical property of carbon fiber.Therefore, the skin-core structure that reduces thermal oxidation stability chemical fibre dimension is the effective way that improves the carbon fiber mechanical property.In the thermal oxidation stability process, oxidation reaction is to cause fiber to form the main factor of skin-core structure radially inhomogeneous of fiber.Therefore the thermal oxidation stability degree of controlling thermal oxidation stability chemical fibre dimension is most important; The judgement thermal oxidation stability chemical fibre dimension degree methods that exists at present concentrates on the mensuration of the density, oxygen content, skin-core structure of thermal oxidation stability chemical fibre dimension etc.; Perhaps adopt cyclisation degree, aromatisation index to come the simple thermal oxidation stability degree of weighing; These methods are relatively single, and the validity that instructs for technology is worth discussion; Consider that thermal oxidation stability oxysome volume concentrations is great to the oxidation reaction influence, and adopt present method to be difficult to the regulation and control of single oxysome volume concentrations are difficult to control and realize.So this patent proposed a kind of novel, effectively regulate and control the method that the thermal oxidation stability chemical fibre is tieed up thermal oxidation stability oxysome volume concentrations jointly through cyclisation degree (η) and aromatisation index (AI); Corrected forefathers only through the deficiency of cyclisation degree or aromatisation index, remedied blank through cyclisation degree and aromatisation index regulation and control thermal oxidation stability gasification atmosphere.Come together effectively to weigh the thermal oxidation stability degree of PAN fiber in thermal oxidation stabilityization through cyclization level data η and degree of oxidation data AI; And through cyclisation degree (η) and two-parameter thermal oxidation stability metallization processes oxygen concentration and other technological parameters of instructing of aromatisation index (AI), for the thermal oxidation stability chemical fibre dimension that obtains high-quality provides new basis for estimation and criterion.
Summary of the invention
The object of the invention is intended to two extents of reaction (cyclization degree and oxidation reaction degree) the comprehensive regulation thermal oxidation stability oxysome volume concentrations through thermal oxidation stability chemical fibre dimension; And guide the thermal oxidation stability metallization processes; Thereby avoid the formation of thermal oxidation stability chemical fibre dimension skin-core structure; Corrected the only deficiency through cyclisation degree or aromatisation index of forefathers; Remedied blank, made control oxysome volume concentrations obtain the requirement of thermal oxidation stability chemical fibre dimension and preparation high-strength carbon fibre through a kind of effective method through cyclisation degree and aromatisation index regulation and control thermal oxidation stability gasification atmosphere.Through confirm the visible Fig. 1 of thermal oxidation stability oxysome volume concentrations through cyclisation degree (η); Confirm that through aromatisation index (AI) thermal oxidation stability oxysome volume concentrations sees Fig. 2.
The present invention provides a kind of preparation method of high-strength carbon fiber; It is characterized in that; With the cyclisation degree (η) of thermal oxidation stability chemical fibre dimension is 82 ± 5% to be 65 ± 5% serve as to regulate and control foundations with aromatisation index (AI); The oxysome volume concentrations of control thermal oxidation stability gasification atmosphere is 21.8 ± 1%, and the control method of thermal oxidation stability process oxygen concentration is incorporated in the preparation process of carbon fiber, prepares high-intensity carbon fiber.
The η of thermal oxidation stability chemical fibre dimension and AI numerical value adopt infrared spectrum and X-ray diffraction analysis to measure respectively, thermal oxidation stability chemical fibre dimension are rubbed be short fiber, and 60 ℃ of oven dry 72h carry out infrared spectrum analysis, obtain the infrared signature peak data; Carry out X-ray diffraction analysis, obtain the characteristic diffraction peak data.Computing formula is: η=0.29*I
1630/ (0.29*I
1630+ I
2240), AI=I
22.5/ (I
22.5+ I
17).I wherein
1630Be 1630cm
-1The place-C=N stretching vibration characteristic absorption peak intensity, I
2240Be 2240cm
-1The place-the characteristic absorption peak intensity of C ≡ N stretching vibration; I
22.5Being that fiber (100) crystal face diffraction maximum ° is located in 2 θ=17, is the characteristic diffraction peak of cyano functional group, I
22.5It is the characteristic diffraction peak of the 2 θ=22.5 ° trapezium structure of locating to form in the fiber.
Under 180 ~ 300 ℃ thermal oxidation stability condition, the polyacrylonitrile copolymer fibre is carried out thermal oxidation stabilityization and follow-up 300 ~ 1600 ℃ of conventional carbonization treatment; Obtain the carbon fiber that TENSILE STRENGTH is higher than 3.75GPa, a certain temperature spot or a certain temperature range inner control carrier of oxygen volume concentrations are 21.8 ± 1% under described thermal oxidation stability condition.
Above-mentioned PAN copolymer fibre tow can adopt the fiber of dry method, wet method or dried wet method spinning, and fibre bundle can be 1 ~ 320K.Copolymer also contains one or more polymer monomers in the above-mentioned PAN fibre bundle except that containing acrylonitrile monemer: acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and ester class thereof, acrylamide, methylene succinic acid, metering system elder generation acid amides, acrolein, MAL, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone etc.
With the preparation carbon fiber be cured as strip with epoxy resin, solvent and the gluing of curing agent mixing material after, carry out the preparation of sample with epoxy resin and curing agent, after specimen preparation is good, fibre bundle is carried out Mechanics Performance Testing.
Effect of the present invention: adopt infrared spectrometer and X-ray diffractometer that the cyclization degree and the oxidation reaction degree of thermal oxidation stability chemical fibre dimension are analyzed.The result shows, when cyclisation degree (η) be 82 ± 5% and aromatisation index (AI) be in 65 ± 5% scopes time, thermal oxidation stability oxysome volume concentrations is 21.8 ± 1%, the TENSILE STRENGTH of the carbon fiber that draws all can surpass 3.75GPa.Prove through instance, thus confirm the oxysome volume concentrations that the thermal oxidation stability chemical fibre is tieed up through cyclisation degree (η) and aromatisation index (AI), and control the thermal oxidation stability metallization processes through the oxysome volume concentrations.
Description of drawings
Fig. 1 confirms thermal oxidation stability oxysome volume concentrations through cyclisation degree (η);
Fig. 2 confirms thermal oxidation stability oxysome volume concentrations through aromatisation index (AI).
The specific embodiment
Further specify the present invention below in conjunction with instance, but not as to limitation of the present invention.
Obtain to carry out infrared analysis and X-ray diffraction analysis after the thermal oxidation stability chemical fibre dimension, can obtain each item numerical value of characteristic peak intensity.
Cyclisation degree (η) and aromatisation index (AI) can be obtained according to formula in claims 1, confirm thermal oxidation stability oxysome volume concentrations with this.
Embodiment 1: selecting the tow of commercially available Britain CourtauldS company wet method spinning is the 3k copolymer fibre; Its copolymer composition (by weight) be: acrylonitrile 96%, methylene succinic acid 1%, methyl acrylate 3%; Equilibrium moisture content 0.67%; In 180 ℃, 210 ℃, 230 ℃, 253 ℃, 273 ℃ five sections warm areas, carry out the thermal oxidation stability processing; Control in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.7% in the thermal oxidation stability gasification atmosphere, the time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 10%, obtains thermal oxidation stability chemical fibre dimension.The thermal oxidation stability chemical fibre is tieed up under protection of nitrogen gas, low-temperature carbonization under 350 ℃, 480 ℃, 580 ℃, the 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+3% degree of draft, apply-3% degree of draft under 1300 ℃ of temperature, high temperature cabonization 2min obtains carbon fiber.Thermal oxidation stabilityization is rubbed into short fiber, carry out infrared spectrum analysis and X-ray diffraction analysis.The carbon fiber of preparation is cured as strip with the gluing of epoxy resin 618/ acetone/triethylene tetramine (10:20:1) liquid, according to GB GB3362-82 corresponding carbon fiber sample is carried out Mechanics Performance Testing again.
Embodiment 2: the thermal oxidation stability gradient temperature becomes 180 ℃, 200 ℃, 240 ℃, 260 ℃, 275 ℃; Control in 260 ℃ of warm areas that the carrier of oxygen volume concentrations is 20.9% in the thermal oxidation stability gasification atmosphere, the time of staying is respectively 4min, 18min, 15min, 13min, 10min, amounts to 60min; The thermal oxidation stability draw ratio becomes 12%.Used PAN copolymer fibre and other operating procedures are all with instance 1.
Embodiment 3: the thermal oxidation stability gradient temperature becomes 180 ℃, 210 ℃, 230 ℃, 250 ℃, 270 ℃; Control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 21% in the thermal oxidation stability gasification atmosphere, the time of staying is respectively 4min, 20min, 15min, 25min, 20min, amounts to 80min; The thermal oxidation stability draw ratio becomes 13%.Used PAN copolymer fibre and other operating procedures are all with instance 1.
Embodiment 4: the thermal oxidation stability gradient temperature becomes 180 ℃, 215 ℃, 233 ℃, 253 ℃, 275 ℃; Control in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.5% in the thermal oxidation stability gasification atmosphere, the time of staying is respectively 4min, 20min, 15min, 25min, 20min, amounts to 80min; The thermal oxidation stability draw ratio becomes 8%.Low-temperature carbonization under 350 ℃, 480 ℃, 580 ℃, 680 ℃ temperature, the time of staying is respectively 2min, 2min, 2min, 2min, amounts to 8min; Apply+3% degree of draft, apply-3% degree of draft under 1300 ℃ of temperature, high temperature cabonization 3min obtains carbon fiber.Used PAN copolymer fibre and other operating procedures are all with instance 1.
Embodiment 5: control in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.4% in the thermal oxidation stability gasification atmosphere, low-temperature carbonization applies+4% degree of draft, applies-4% degree of draft under 1300 ℃ of temperature, and high temperature cabonization 5min obtains carbon fiber.Used PAN copolymer fibre and other operating procedures are all with instance 4.
Embodiment 6: control in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.7% in the thermal oxidation stability gasification atmosphere, used PAN copolymer fibre and other operating procedures are all with instance 4.
Embodiment 7: control in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.5% in the thermal oxidation stability gasification atmosphere, used PAN copolymer fibre and other operating procedures are all with instance 5.
Embodiment 8: adopt commercially available Jilin Chemical Industry Company synthetic resin plant to do the 6K tow PAN copolymer fibre of wet method spinning; The condensate that fiber uses is acrylonitrile: methyl acrylate: α-chloropropene; Use amount is respectively 92:6:2 (wt%), and equilibrium moisture content is 0.72%, and density is 1.182g/cm
3Anti-, intensity is 5.62CN/dtex, and extension at break is 15.2%.In 180 ℃, 215 ℃, 235 ℃, 250 ℃, 270 ℃ five sections warm areas, carry out the thermal oxidation stability processing; Control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.5% in the thermal oxidation stability gasification atmosphere; The time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 12%, obtains thermal oxidation stability chemical fibre dimension.The thermal oxidation stability chemical fibre is tieed up under protection of nitrogen gas, low-temperature carbonization under 350 ℃, 480 ℃, 580 ℃, the 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+4% degree of draft, apply-2% degree of draft under 1300 ℃ of temperature, high temperature cabonization 2min obtains carbon fiber.Thermal oxidation stabilityization is rubbed into short fiber, carry out infrared spectrum analysis and X-ray diffraction analysis.The carbon fiber of preparation is cured as strip with the gluing of epoxy resin 618/ acetone/triethylene tetramine (10:20:1) liquid, according to GB GB3362-82 corresponding carbon fiber sample is carried out Mechanics Performance Testing again.
Embodiment 9: in 180 ℃, 210 ℃, 230 ℃, 250 ℃, 270 ℃ five sections warm areas, carry out the thermal oxidation stability processing; Control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.6% in the thermal oxidation stability gasification atmosphere; The time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 83min; Degree of draft is 14%, obtains thermal oxidation stability chemical fibre dimension.Used PAN copolymer fibre and other operating procedures are all with instance 8.
Embodiment 10: in 185 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃ five sections warm areas, carry out the thermal oxidation stability processing; Control in 260 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.6% in the thermal oxidation stability gasification atmosphere; The time of staying is respectively 1min, 15min, 20min, 25min, 20min, amounts to 81min; Degree of draft is 14%, obtains thermal oxidation stability chemical fibre dimension.Used PAN copolymer fibre and other operating procedures are all with instance 8.
Embodiment 11: control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.6% in the thermal oxidation stability gasification atmosphere, thermal oxidation stability process draw ratio is 8%, obtains thermal oxidation stability chemical fibre dimension.Used PAN copolymer fibre and other operating procedures are all with instance 8.
Embodiment 12: control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.0% in the thermal oxidation stability gasification atmosphere, thermal oxidation stability process draw ratio is 6%, obtains thermal oxidation stability chemical fibre dimension.Used PAN copolymer fibre and other operating procedures are all with instance 10.
Embodiment 13: control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.2% in the thermal oxidation stability gasification atmosphere, low-temperature carbonization applies+4% degree of draft, applies-4% degree of draft under 1300 ℃ of temperature, and high temperature cabonization 5min obtains carbon fiber.Used PAN copolymer fibre and other operating procedures are all with instance 10.
Embodiment 14: control in 250 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.5% in the thermal oxidation stability gasification atmosphere, used PAN copolymer fibre and other operating procedures are all with instance 8.
Embodiment 15: the 12kPAN copolymer fibre that adopts Oil of Shanghai Petrochemical Company company dry method spinning; The condensate that fiber uses is acrylonitrile: the hydroxyalkyl acrylonitrile: the metering system benzylacetone; Use amount is respectively 93:6:1 (wt%), and equilibrium moisture content is 0.52%, and density is 1.190g/cm
3Intensity is 6.62CN/dtex; Extension at break is 16.4%, in 180 ℃, 220 ℃, 235 ℃, 255 ℃, 267 ℃ five sections warm areas, carries out the thermal oxidation stability processing, controls in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 21% in the thermal oxidation stability gasification atmosphere; The time of staying is respectively 3min, 20min, 20min, 20min, 20min, amounts to 93min; Degree of draft is 4%, obtains thermal oxidation stability chemical fibre dimension.The thermal oxidation stability chemical fibre is tieed up under protection of nitrogen gas, low-temperature carbonization under 350 ℃, 480 ℃, 580 ℃, the 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+5% degree of draft, apply-2% degree of draft under 1300 ℃ of temperature, high temperature cabonization 2min obtains carbon fiber.Other technological parameters and operating procedure be all with instance 1,
Embodiment 16: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.1% in the thermal oxidation stability gasification atmosphere, thermal oxidation stability process draw ratio is 7%, and precursor kind and other technological parameters and operating procedure are all with instance 15.
Embodiment 17: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.3% in the thermal oxidation stability gasification atmosphere, thermal oxidation stability process draw ratio is 9%, and precursor kind and other technological parameters and operating procedure are all with instance 15.
Embodiment 18: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.8% in the thermal oxidation stability gasification atmosphere, thermal oxidation stability process draw ratio is 11%, and precursor kind and other technological parameters and operating procedure are all with instance 15.
Embodiment 19: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.7% in the thermal oxidation stability gasification atmosphere; The thermal oxidation stability chemical fibre is tieed up under protection of nitrogen gas; Low-temperature carbonization under 350 ℃, 480 ℃, 580 ℃, the 680 ℃ temperature, the time of staying is respectively 1min, 1min, 1min, 1min, amounts to 4min; Apply+6% degree of draft, apply-4% degree of draft under 1300 ℃ of temperature, high temperature cabonization 2min, precursor kind and other technological parameters and operating procedure are all with instance 15.
Embodiment 20: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 20.8% in the thermal oxidation stability gasification atmosphere, precursor kind and other technological parameters and operating procedure are all with instance 15.
Embodiment 21: control in 255 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.8% in the thermal oxidation stability gasification atmosphere, precursor kind and other technological parameters and operating procedure are all with instance 19.
Embodiment 22: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and the condensate that fiber uses is acrylonitrile: acrylamide: the metering system benzylacetone, use amount is respectively: 92:6:2 (wt%), equilibrium moisture content is 0.58%, density is 1.193g/cm
3, intensity is 6.02cN/dtex, and extension at break is 17.4%, controls in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 21.6% in the thermal oxidation stability gasification atmosphere, and the thermal oxidation stability draw ratio becomes 3%, and other technological parameters and operating procedure are all with instance 1.
Embodiment 23: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and the thermal oxidation stability draw ratio becomes 6%, and other technological parameters and operating procedure are all with instance 1.
Embodiment 24: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, and the thermal oxidation stability draw ratio becomes 9%, control that the carrier of oxygen volume concentrations is 21.4% in the interior thermal oxidation stability gasification atmosphere of 253 ℃ of warm areas, and other technological parameters and operating procedure are all with instance 1.
Embodiment 25: the 24kPAN copolymer fibre that adopts U.S. Hexcel company to produce, control that the carrier of oxygen volume concentrations is 22.5% in the interior thermal oxidation stability gasification atmosphere of 253 ℃ of warm areas, and the thermal oxidation stability draw ratio becomes 12%, and other technological parameters and operating procedure are all with instance 1.
Embodiment 26: the 48kPAN copolymer fibre that adopts Japanese rising sun company to become to produce, and the condensate that fiber uses is acrylonitrile: allyl chloride: α-chloropropene, use amount is respectively: 92:7:1 (wt%), equilibrium moisture content is 0.69%, density is 1.183g/cm
3, intensity is 6.72cN/dtex, and extension at break is 19.4%, and the thermal oxidation stability draw ratio becomes 12%, controls in 253 ℃ of warm areas that the carrier of oxygen volume concentrations is 22.6% in the thermal oxidation stability gasification atmosphere, and other technological parameters and operating procedure are all with instance 1.
Embodiment 27: the 48kPAN copolymer fibre that adopts Japanese rising sun company to become to produce, and the thermal oxidation stability draw ratio becomes 6%, and other technological parameters and operating procedure are all with instance 1.
Embodiment 28: the 48kPAN copolymer fibre that adopts Japanese rising sun company to become to produce, and the thermal oxidation stability draw ratio becomes 1%, and other technological parameters and operating procedure are all with instance 4.Cyclisation degree η and aromatisation Index A I result such as table 1 with the TENSILE STRENGTH of the carbon fiber that obtains under the different condition in the foregoing description and thermal oxidation stability chemical fibre dimension.
Table 1: embodiment thermal oxidation stability chemical fibre dimension and carbon fiber numerical value
Claims (5)
1. the preparation method of a high-strength carbon fiber; It is characterized in that; With the cyclisation degree of thermal oxidation stability chemical fibre dimension is 82 ± 5% to be 65 ± 5% serve as the regulation and control foundations with the aromatisation index, and the oxysome volume concentrations of control thermal oxidation stability gasification atmosphere is 21.8 ± 1%, prepares high-strength carbon fiber.
2. according to the method for claim 1; It is characterized in that; The cyclisation degree of thermal oxidation stability chemical fibre dimension and aromatisation exponential number adopt infrared spectrum and X-ray diffraction analysis to measure respectively, thermal oxidation stability chemical fibre dimension are rubbed be short fiber, 60 ℃ of oven dry 72h; Carry out infrared spectrum analysis, obtain the infrared signature peak data; Carry out X-ray diffraction analysis, obtain the characteristic diffraction peak data;
Computing formula is: η=0.29*I
1630/ (0.29*I
1630+ I
2240), AI=I
22.5/ (I
22.5+ I
17), I wherein
1630Be 1630cm
-1The place-C=N stretching vibration characteristic absorption peak intensity, I
2240Be 2240cm
-1The place-the characteristic absorption peak intensity of C ≡ N stretching vibration; I
22.5Being that fiber (100) crystal face diffraction maximum ° is located in 2 θ=17, is the characteristic diffraction peak of cyano functional group, I
22.5It is the characteristic diffraction peak of the 2 θ=22.5 ° trapezium structure of locating to form in the fiber.
3. according to the method for claim 1; It is characterized in that; Under 180 ~ 300 ℃ thermal oxidation stability condition, the polyacrylonitrile copolymer fibre is carried out thermal oxidation stabilityization and follow-up 300 ~ 1600 ℃ of conventional carbonization treatment; Obtain the carbon fiber that TENSILE STRENGTH is higher than 3.75GPa, a certain temperature spot or a certain temperature range inner control carrier of oxygen volume concentrations are 21.8 ± 1% under described thermal oxidation stability condition.
4. according to the method for claim 3, it is characterized in that polyacrylonitrile copolymer fibre tow adopts the fiber of dry method, wet method or dried wet method spinning, fibre bundle is 1 ~ 320K.
5. according to the method for claim 3; It is characterized in that; The polyacrylonitrile copolymer fibre also contains one or more polymer monomers except that containing acrylonitrile monemer: acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, hydroxyalkyl acrylonitrile, hydroxyalkyl acrylic acid and ester class thereof, acrylamide, methylene succinic acid, metering system elder generation acid amides, acrolein, MAL, allyl chloride, α-chloropropene, diacetone acrylamide, metering system benzylacetone, vinyl pyrrolidone.
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| CN111304784A (en) * | 2020-03-13 | 2020-06-19 | 北京化工大学 | Preparation method of large-diameter high-strength medium-modulus carbon fiber and high-strength high-modulus carbon fiber |
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